Ruthenium hydride and vinyl complexes supported by nitrogen-oxygen mixed-donor ligands

Article abstract of DOI:10.1016/j.ica.2005.04.036

The Schiff base, 2-chlorophenylsalicylaldimine (HL₁), is formed readily from salicylaldehyde and 2-chloroaniline. After deprotonation, this ligand is found to react as a bidentate mixed-donor chelate with the complexes [RuRCl(CO)(BTD)(PPh₃)₂] (R = H, CHCHC₆H ₅, CHCHC₆H₄Me-4, CHCH^tBu, CCCPhCHPh; BTD = 2,1,3-benzothiadiazole) to form the compounds [RuR(L₁)(CO) (PPh₃)₂] through displacement of the chloride and BTD ligands. An analogous reaction occurs with the osmium complex [OsHCl(CO)(BTD)(PPh₃)₂] to provide [OsH(L ₁)(CO)(PPh₃)₂]. The compound [Ru(CHCHC ₆H₄Me-4)(L₂)(CO)(PPh₃)₂] is formed through reaction of salicylaldehyde (HL₂) with [Ru(CHCHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃) ₂] in the presence of base. Two further ligands were investigated to extend the study to encompass 5- and 4-membered chelates; 8-hydroxyquinoline (HL₃) and 2-hydroxy-4-methylquinoline (HL₄) react with [Ru(CHCHPh)Cl(CO)(BTD)(PPh₃)₂] and [Ru(CHCHC ₆H₄Me-4)Cl(CO)(BTD)(PPh₃)₂] in the presence of base to yield the complexes [Ru(CHCHPh)(L₃)(CO)(PPh ₃)₂] and [Ru(CHCHC₆H₄Me-4)(L ₄)(CO)(PPh₃)₂], respectively. The crystal structure of [Ru(CHCHC₆H₄Me-4)(L₁)(CO)(PPh ₃)₂] is reported.

Full text of DOI:10.1016/j.ica.2005.04.036

Inorganica Chimica Acta 358 (2005) 3218–3226
www.elsevier.com/locate/ica
Ruthenium hydride and vinyl complexes supported by
nitrogen–oxygen mixed-donor ligands
*
James D.E.T. Wilton-Ely , Ming Wang, Sanaz J. Honarkhah, Derek A. Tocher
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
Received 16 February 2005; accepted 26 April 2005
Dedicated to Prof. Dr. Hubert Schmidbaur in recognition of his vast contribution to so many areas of inorganic chemistry
Abstract
The Schiff base, 2-chlorophenylsalicylaldimine (HL1), is formed readily from salicylaldehyde and 2-chloroaniline. After deproto-
nation, this ligand is found to react as a bidentate mixed-donor chelate with the complexes [RuRCl(CO)(BTD)(PPh3)2] (R = H,
CH@CHC6H5, CH@CHC6H4Me-4, CH@CHtBu, CC„CPh@CHPh; BTD = 2,1,3-benzothiadiazole) to form the compounds
[RuR(L1)(CO)(PPh3)2] through displacement of the chloride and BTD ligands. An analogous reaction occurs with the osmium com-
plex [OsHCl(CO)(BTD)(PPh3)2] to provide [OsH(L1)(CO)(PPh3)2]. The compound [Ru(CH@CHC6H4Me-4)(L2)(CO)(PPh3)2] is
formed through reaction of salicylaldehyde (HL2) with [Ru(CH@CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] in the presence of base.
Two further ligands were investigated to extend the study to encompass 5- and 4-membered chelates; 8-hydroxyquinoline (HL3)
and 2-hydroxy-4-methylquinoline (HL4) react with [Ru(CH@CHPh)Cl(CO)(BTD)(PPh3)2] and [Ru(CH@CHC6H4Me-
4)Cl(CO)(BTD)(PPh3)2] in the presence of base to yield the complexes [Ru(CH@CHPh)(L3)(CO)(PPh3)2] and [Ru
(CH@CHC6H4Me-4)(L4)(CO)(PPh3)2], respectively. The crystal structure of [Ru(CH@CHC6H4Me-4)(L1)(CO)(PPh3)2] is reported.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Ruthenium; Schiff base; Hydride; Vinyl; Mixed-donor
1. Introduction
[3]), the resulting vinyl complexes [4,5] have been the
subject of much pioneering work by the groups of
Werner and co-workers [6–11], Esteruelas and co-work-
ers [12–24], Santos and co-workers [25–30], and Caul-
ton, Eisenstein and co-workers [31–33] covering
functional group transformation, ligand exchange and
theoretical calculations. The hydride complexes them-
selves are known for their ability to catalyse hydrogena-
tion reactions [34] and the formation of di-ynes [35,36].
A recent indication of the continuing importance of
these starting materials is given by a recent report of
their use in silylation catalysis [37].
The vinyl ligand is an important member of the sig-
ma-organyl ligand family and has attracted significant
interest over the last 40 years. Vinyl complexes are
known for many metals but examples of this ligand
are most commonly found with metals of group 8. This
is largely due to well-established synthetic routes such as
hydrometallation and the reaction of coordinated alky-
nes with electrophiles or nucleophiles [1].
Since the discovery of hydrometallation of alkynes by
the complexes [RuHCl(CO)L2/3] (L = PiPr3, [2] PPh3
Previous work from members of our own group has
concentrated on vinyl complexes supported by bidentate
and tridentate nitrogen and sulfur donor ligands and the
reactions of these complexes [38]. This complemented
*
Corresponding author. Tel.: +44 020 7679 1027; fax: +44 020 7679
7463.
E-mail address: j.wilton-ely@ucl.ac.uk (J.D.E.T. Wilton-Ely).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.04.036

J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
3219
work by other groups exploring the effect of polydentate
donors on the structure and reactivity of vinyl com-
plexes. The majority of this research has concentrated
on the use of symmetrical, bidentate phosphorus
[39,40], nitrogen [41,42] or chalcogen donors [43]. The
work reported here is part of a programme [44,45] to
synthesise vinyl complexes bearing mixed-donor biden-
tate ligands and to investigate their effect on migratory
insertion reactions and hemilabile behaviour in these
complexes.
[Ru(CH@CHtBu)Cl(CO)(BTD)(PPh3)2] [53], [Ru{C-
(C„CPh)@CHPh}Cl(CO)(BTD)(PPh3)2] [54], and [Os-
HCl(CO)(BTD)(PPh3)2] [38e] were prepared according
to published procedures. See Chart 1 for the numbering
scheme used for the Schiff base ligand (HL1).
2.2. Syntheses
2.2.1. Preparation of 2-chlorophenylsalicylaldimine
(HL1)
Schiff bases have been used for many years to coor-
dinate metal ions [46,47]. Interest has been rekindled
recently with reports of their use in catalysts for olefin
polymerisation [48]. Ruthenium Schiff base complexes
have been known for 30 years [49] and have more re-
cently found use in catalysis [49c,50] and biological
applications [51]. Perhaps surprisingly, given the cata-
lytic interest, no ruthenium Schiff base complexes
bearing vinyl ligands have been reported. Here, we
describe the use of a Schiff base ligand and two other
N/O-donor ligands to prepare group 8 hydride and vi-
nyl complexes with 4, 5 and 6-membered mixed-donor
chelates.
Salicylaldehyde (1.00 g, 8.19 mmol) and 2-chloroan-
iline (1.05 g, 8.23 mmol) were placed in a Schlenk flask
and degassed ethanol (50 mL) added. The reaction
was stirred and heated for 30 min until a bright yellow
solution had developed. The solvent volume was re-
duced causing precipitation of an intense yellow prod-
uct. This was filtered and washed with cold ethanol
(5 · 3 mL). Yield: 1.64 g (86%). IR (KBr/nujol):
1620, 1566, 1273, 1188, 1145, 1057, 1030, 980, 945,
1
910 cmꢀ1. H NMR (CDCl3, 500.1 MHz): 6.92 [td, H12
(L1), 1H, J(H12H11/13) = 7.5 Hz, J(H12H10) = 1.2 Hz],
7.03
[dd,
H10(L1),
1H,
7.18
J(H10H11) = 8.7 Hz,
J(H10H12) = 1.2 Hz],
[ddd,
H4(L1),
1H,
J(H4H3) = 8.0 Hz, J(H4H5) = 7.3 Hz, J(H4H6) = 1.6
Hz], 7.20 [dd, H6(L1), 1H, J(H6H5) = 8.0 Hz,
J(H6H4) = 1.6 Hz], 7.29 [ddd, H5(L1), 1H, J(H5H6)
= 8.0 Hz, J(H5H4) = 7.3 Hz, J(H5H3) = 1.4 Hz], 7.37
2. Experimental
2.1. Methods and instrumentation
[dd, H13(L1), 1H, J(H13H12) = 7.7 Hz, J(H13H11)
=
1.7 Hz], 7.38 [td, H11(L1), 1H, J(H11H10/12) = 7.5 Hz,
J(H11H13) = 1.7 Hz] 7.45 [dd, H3(L1), 1H, J(H3H4)
= 7.9 Hz, J(H3H5) = 1.3 Hz], 8.56 [s, H7(L1), 1H],
13.24 [s, OH, 1H] ppm. 13C NMR (CDCl3,
500.1 MHz): 117.3 (C10), 118.9 (C8), 119.0 (C6 + C12),
127.6 (C4), 127.7 (C5), 129.4 (C2), 130.0 (C3), 132.4
(C13), 133.5 (C11), 145.1 (C1), 161.2 (C9), 163.1
(C7) ppm. FAB-MS m/z (abundance) = 231 (100) [M]+,
196 (50) [M ꢀ Cl]+. Anal. Calc. for C13H10ClNO: C,
67.4; H, 4.4; N, 6.1. Found: C, 67.3; H, 4.4; N, 5.9%.
All manipulations were carried out under aerobic con-
ditions using commercially available solvents and re-
agents as received. Infrared spectroscopy was carried
out using a Shimadzu FTIR 8700 spectrometer with
KBr plates and nujol. NMR spectra were obtained at
25 ꢁC (unless stated otherwise) using Bruker AMX-300
(1H: 299.87 MHz, 31P: 121.39 MHz, 13C: 75.40 MHz)
or Bruker DRX-500 (1H: 500.13 MHz, 13C:
125.77 MHz) spectrometers. Spectroscopic features due
to the triphenylphosphine ligands have been omitted to
aid clarity. The term s(br) is used to denote a broadened
singlet resonance. FAB-MS spectra (nitrobenzyl alcohol
matrices) were measured using a VG 70-SB magnetic sec-
tor mass spectrometer. Elemental microanalyses were
performed at University College London. The amount
of solvent of crystallisation was determined by integra-
tion of 1H NMR spectra. The complexes [RuHCl
(CO)(PPh3)3] [3], [RuHCl(CO)(BTD)(PPh3)2] [52],
2.2.2. Preparation of [RuH(L1)(CO)(PPh3)2] (1)
[RuHCl(CO)(BTD)(PPh3)2] (100 mg, 0.121 mmol)
and 2-chlorophenylsalicylaldimine (HL1) (30 mg,
0.129 mmol) were suspended in dichloromethane
(20 mL) and treated with sodium methoxide (13 mg,
0.241 mmol) in ethanol (10 mL). A colour change was
observed from dark orange to yellow. The reaction
was stirred for 1 h and the solvent volume reduced to
ca. 10 mL. The flask was kept at ꢀ20 ꢁC for 4 h and
the resulting yellow precipitate filtered, washed with
cold ethanol (5 mL) and hexane (10 mL). Yield: 57 mg
(53%). IR (KBr/nujol): 1975 [m(RuH)], 1906 [m(CO)],
[Ru(CH@CHC6H4CH3-4)Cl(CO)(BTD)(PPh3)2]
[53],
1604, 1195, 1142, 972 cmꢀ1
.
31P NMR (C6D6): 58.5
1
[s(br), PPh3] ppm. H NMR (C6D6): ꢀ10.77 [td, RuH,
1H, JHP = 21.4 Hz, JHH7 = 2.9 Hz], 6.15 [t, (H12)L1,
1H, JHH = 7.3 Hz], 6.30 [d, (H10)L1, 1H, JHH = 8.4 Hz],
6.44 [dd, (H6)L1, 1H, JHH = 7.9 Hz, JHH = 1.8 Hz], 6.58
Chart 1. 2-chlorophenylsalicylaldimine (HL1) with numbering scheme.

3220
J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
[dt, (H4/5)L1, 1H, JHH = 7.8 Hz, JHH = 1.5 Hz], 6.83 [m,
(H11 + H13)L1, 1H + 1H], 6.9 [dd, (H3)L1, 1H, JHH
8.00 Hz, JHH = 1.4 Hz], 6.96–7.80 [m, C6H5 + (H4/5)L1,
30H + 1H], 7.54 [d, H7(L1), 1H, JH7H = 2.9 Hz] ppm.
FAB-MS m/z (abundance) = 884 (0.3) [M]+, 653 (0.7)
[M ꢀ L1]+. Anal. Calc. for C50H40ClNO2P2Ru: C, 67.8;
H, 4.6; N, 1.6. Found: C, 67.7; H, 4.7; N, 1.3%.
C6H5, 2H, JHH = 7.5 Hz], 7.00–7.45 [m, PC6H5 +
(H3,4,5,7,11,13)L1, 30H + 6H], 8.25 [dt, Ha, 1H,
JHH = 16.9 Hz, JHP = 3.1 Hz] ppm. FAB-MS m/z (abun-
dance) = 988 (5) [M]+, 884 (6) [M ꢀ vinyl]+, 725 (40)
[M ꢀ PPh3]+, 697 (6) [M ꢀ CO ꢀ PPh3]+, 623 (15)
[M ꢀ vinyl ꢀ PPh3]+, 594 (20) [M ꢀ CO ꢀ vinyl ꢀ
PPh3]+. Anal. Calc. for C58H46- ClNO2P2Ru: C, 66.1;
H, 4.5; N, 1.3. Found: C, 65.5; H, 4.4; N, 1.6%.
=
2.2.3. Preparation of [OsH(L1)(CO)(PPh3)2] (2)
[OsHCl(CO)(BTD)(PPh3)2] (50 mg, 0.055 mmol) and
HL1 (14 mg, 0.060 mmol) were suspended in dichloro-
methane (20 mL) and treated with sodium methoxide
(6 mg, 0.111 mmol) in ethanol (10 mL). The colour of
the solution lightened during stirring for 30 min. The
solvent was reduced until precipitation of an orange
product had started. The flask was kept at ꢀ20 ꢁC for
4 h and the resulting precipitate filtered, washed with
cold ethanol (5 mL) and hexane (10 mL). Yield: 37 mg
(69%). IR (KBr/nujol): 2073 [m(OsH)], 1888 [m(CO)],
2.2.5. Preparation of [Ru(CH@CHC6H4Me-4)(L1)
(CO)(PPh3)2] (4)
[Ru(CH@CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (100
mg, 0.106 mmol) and HL1 (27 mg, 0.117 mmol) were
suspended in dichloromethane (20 mL) and treated
with sodium methoxide (11 mg, 0.204 mmol) in ethanol
(10 mL). The mixture was stirred for 1 h and then all
solvent was removed. The residue was taken up in a
minimum quantity of dichloromethane and filtered
through diatomaceous earth. The solvent was reduced
to ca. 5 mL and diethyl ether (40 mL) added gradually
to precipitate the orange product. This was washed with
diethyl ether (10 mL) and hexane (10 mL). Yield: 68 mg
(64%). IR (KBr/nujol): 1911 [m(CO)], 1607, 1578, 1530,
1607, 1580, 1531, 1360, 1185, 1146, 928 cmꢀ1 31P
.
NMR (C6D6, 25ꢁC): 18.0, 27.3 [AB, PPh3, JAB = 320
Hz] ppm. 31P NMR (C6D6, 60 ꢁC): 21.8 [s(br), PPh3]
ppm. 1H NMR (CDCl3): ꢀ11.68 [td, OsH, 1H,
JHP = 19.5 Hz, JHH7 = 2.4 Hz], 6.14 [t, (H12)L1, 1H,
JHH = 7.1 Hz], 6.21 [d, (H10)L1, 1H, JHH = 8.6 Hz],
6.46 [dd, (H6)L1, 1H, JHH = 7.8 Hz, JHH = 1.7 Hz],
6.56 [td, (H4/5)L1, 1H, JHH = 7.6 Hz, JHH = 1.3 Hz],
6.79 [dd, (H3)L1, 1H, JHH = 8.0 Hz, JHH = 1.3 Hz],
6.86 [m, (H11)L1 + (H4/5)L1, 1H + 1H], 6.95–7.82 [m,
C6H5, 30H], 7.30 [dd, (H13)L1, 1H, JHH = 8.1 Hz,
JHH = 1.4 Hz], 7.57 [d, H7(L1), 1H, JH7H = 2.4 Hz]
ppm. FAB-MS m/z (abundance) = 975 (18) [M]+, 743
(4) [M ꢀ L1]+, 713 (15) [M ꢀ PPh3]+, 685 (5) [M ꢀ
1324, 1174, 1147, 972, 924, 828 cmꢀ1
.
31P NMR
(CDCl3): 31.0 [s(br), PPh3] ppm. 1H NMR (CDCl3):
2.21 [s, CH3, 3H], 5.74 [d, Hb, 1H, JHH = 16.8 Hz],
6.10 [t, (H12)L1, 1H, JHH = 7.1 Hz], 6.38 [m,
(H6)L1 + (H10)L1, 1H + 1H], 6.40, 6.95 [AB, C6H4,
4H, JAB = 7.5 Hz], 6.65 [t, (H4)L1, 1H, JHH = 7.2 Hz],
6.79 [d, (H3)L1, 1H, JHH = 7.8 Hz], 6.89 [m, (H11)L1,
1H], 7.05–7.42 [m, C6H5 + (H5,7,13)L1, 30H + 3H], 8.13
[dt, Ha, 1H, JHH = 16.8 Hz, JHH = 3.3 Hz] ppm. FAB-
MS m/z (abundance) = 1001 (0.1) [M]+, 855 (2)
[M ꢀ vinyl]+, 739 (15) [M ꢀ PPh3]+, 594 (5) [M ꢀ CO ꢀ
vinyl ꢀ PPh3]+. Anal. Calc. for C59H48ClNO2-
P2Ru Æ 2CH2Cl2: C, 62.5; H, 4.4; N, 1.2. Found: C,
62.5; H, 4.2; N, 1.1%.
COPPh3]+.
Anal.
Calc.
for
C50H40ClNO2Os-
P2 Æ 0.75CH2Cl2: C, 58.7; H, 4.0; N, 1.4. Found: C,
58.9; H, 3.9; N, 1.4%.
2.2.4. Preparation of [Ru(CH@CHPh)(L1)(CO)-
(PPh3)2] (3)
2.2.6. Preparation of [Ru(CH@CHtBu)(L1)(CO)
(PPh3)2] (5)
[Ru(CH@CHPh)Cl(CO)(PPh3)2] (100 mg, 0.126 mmol)
and HL1 (32 mg, 0.138 mmol) were suspended in dichlo-
romethane (20 mL) and treated with sodium methoxide
(13 mg, 0.241 mmol) in ethanol (10 mL). A colour
change was observed from deep red to orange. The mix-
ture was stirred for 1 h to yield an orange solution. The
solvent was reduced until precipitation of the yellow
product was complete. This was washed with water
(5 mL), cold ethanol (5 mL) and hexane (10 mL). Yield:
71 mg (57%). IR (KBr/nujol): 1909 [m(CO)], 1609, 1578,
[Ru(CH@CHtBu)Cl(CO)(BTD)(PPh3)2]
(100 mg,
0.110 mmol) and HL1 (28 mg, 0.121 mmol) were sus-
pended in dichloromethane (20 mL) and treated with so-
dium methoxide (12 mg, 0.222 mmol) in ethanol
(10 mL). The mixture was stirred for 1 h and then all
solvent was removed. The residue was taken up in a
minimum quantity of dichloromethane and filtered
through diatomaceous earth. The solvent was reduced
to ca. 5 mL and diethyl ether (40 mL) added gradually
to precipitate the brown product. This was washed with
diethyl ether (10 mL) and hexane (10 mL). Yield: 68 mg
(64%). IR (KBr/nujol): 1902 [m(CO)], 1607, 1574, 1335,
1549, 1530, 1332, 1188, 1180, 1148, 925, 840, 810 cmꢀ1
.
1
31P NMR (CDCl3): 29.8 [s(br), PPh3] ppm. H NMR
(CDCl3): 5.79 [d, Hb, 1H, JHH = 16.9 Hz], 6.09 [t,
(H12)L1, 1H, JHH = 6.9 Hz], 6.38 [dd, (H6)L1, 1H,
JHH = 7.87 Hz, JHH = 1.7 Hz], 6.44 [d, (H10)L1, 1H,
JHH = 8.6 Hz], 6.50 [d, ortho-C6H5, 2H, JAB = 7.3 Hz],
6.82 [t, para-C6H5, 1H, JHH = 7.2 Hz], 6.97 [t, meta-
1254, 1173, 1146, 976, 924, 854 cmꢀ1
.
31P NMR
(CDCl3): 26.6 [s(br), PPh3] ppm. 1H NMR (CDCl3):
0.37 [s, CH3, 9H], 4.96 [dt, Hb, 1H, JHH = 16.8 Hz,
JHH = 2.0 Hz], 6.10 [td, (H12)L1, 1H, JHH = 7.3 Hz,

J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
3221
JHH = 1.0 Hz], 6.54 [m, (H6)L1 + (H10)L1, 1H + 1H],
6.77 [dd, (H3)L1, 1H, JHH = 8.0 Hz, JHH = 1.5 Hz],
6.85–7.05 [m, C6H5 + (H4,5,7,11,13)L1 + Ha, 30H +
5H + 1H], 8.13 [dt, Ha, 1H, JHH = 16.8 Hz,
JHH = 3.3 Hz] ppm. FAB-MS m/z (abundance) = 737
(1) [M ꢀ L1]+, 705 (33) [M ꢀ PPh3]+, 677 (10)
[M ꢀ CO ꢀ PPh3]+, 653 (3) [M ꢀ vinyl ꢀ L1]+, 625 (7)
[M ꢀ vinyl ꢀ CO ꢀ L1]+, 594 (10) [M ꢀ vinyl ꢀ CO ꢀ
PPh3]+. Anal. Calc. for C56H50ClNO2P2Ru Æ 0.5CH2Cl2:
C, 67.2; H, 5.1; N, 1.4. Found: C, 67.0; H, 5.0; N, 1.1%.
[t, H4/5(L2), 1H, JHH = 8.3 Hz], 6.52, 6.85 [AB, C6H4,
4H, JAB = 8.0 Hz], 6.91 [m, H4/5(L2), 1H], 7.19–7.49
[m, C6H5 + H2/6(L2), 30H + 1H], 8.10 [dt, Ha, 1H,
JHH = 16.2 Hz, JHP = 2.8 Hz], 8.12 [s, CHO, 1H] ppm.
FAB-MS m/z (abundance) = 891 (12) [M]+, 774 (4)
[M ꢀ vinyl]+, 629 (37) [M ꢀ PPh3]+, 601 (5)
[M ꢀ CO ꢀ PPh3]+. Anal. Calc. for C66H50ClNO2-
P2Ru Æ 1.25CH2Cl2: C, 67.7; H, 4.4; N, 1.2. Found: C,
67.4; H, 4.6; N, 0.9%.
2.2.9. Preparation of [Ru(CH@CHPh)(L3)(CO)
(PPh3)2] (8)
2.2.7. Preparation of [Ru{C(C„CPh)@CHPh}
(L1)(CO)(PPh3)2] (6)
[Ru(CH@CHPh)Cl(CO)(BTD)(PPh3)2] (100 mg, 0.108
mmol) and 8-hydroxyquinoline (HL3) (17 mg, 0.117
mmol) were dissolved in dichloromethane (20 mL) and
treated with sodium methoxide (11 mg, 0.204 mmol) in
ethanol (10 mL). A colour change was observed from
deep red to yellow. The mixture was stirred for 1 h
and then all solvent removed under reduced pressure.
The residue was taken up in a minimum volume of
dichloromethane and filtered through diatomaceous
earth to remove NaCl and excess NaOMe. The solvent
volume was reduced to ca. 5 mL and diethyl ether
(10 mL) was added and the flask cooled at ꢀ20 ꢁC for
3 h. The resulting yellow precipitate was filtered, washed
with cold diethylether (5 mL) and hexane (10 mL).
Yield: 65 mg (67%). IR (KBr/nujol): 1908 [m(CO)],
[Ru{C(C„CPh)@CHPh}Cl(CO)(BTD)(PPh3)2] (100
mg, 0.097 mmol) and HL1 (25 mg, 0.108 mmol) were
suspended in dichloromethane (20 mL) and treated
with sodium methoxide (11 mg, 0.204 mmol) in ethanol
(10 mL). This gave rise to a colour change from an or-
ange solution to yellow. The mixture was stirred for
30 min to yield a yellow solution. All solvent was re-
moved and the residue taken up in a minimum volume
of dichloromethane. This solution was filtered through
diatomaceous earth and again all solvent was removed.
Diethylether (20 mL) was added and the flask triturated
in an ultrasound bath to yield a yellow product which
was filtered and washed with diethylether (10 mL) and
hexane (10 mL). Yield: 68 mg (65%). IR (KBr/nujol):
2154 [m(C„C)], 1921 [m(CO)], 1614, 1593, 1313, 1185,
1568, 1323, 1261 cmꢀ1 31P NMR (C6D6): 30.8 [s,
.
1146, 975, 845 cmꢀ1
.
31P NMR (CDCl3): 31.7 [s(br),
PPh3] ppm. 1H NMR (C6D6): 6.17 [dd, L3, 1H,
JHH = 8.3 Hz, JHH = 4.7 Hz], 6.32 [dd, L3, 1H,
JHH = 7.1 Hz, JHH = 1.91 Hz], 6.75 [dt, Hb, 1H,
JHH = 16.8 Hz, JHP = 2.1 Hz], 6.89, 7.14, 7.66 [m · 3,
C6H5 + L3, 30H + 3H], 7.88 [d, L3, 1H, JHH unresolved],
8.94 [dt, Ha, 1H, JHH = 16.8 Hz, JHP = 3.4 Hz] ppm.
FAB-MS m/z (abundance) = 915 (5) [M]+, 798 (3)
[M ꢀ vinyl]+, 653 (12) [M ꢀ PPh3]+, 625 (4) [M ꢀ CO
ꢀ PPh3]+, 508 (4) [M ꢀ L3 ꢀ PPh3]+. Anal. Calc. for
C55H45NO2P2Ru: C, 72.2; H, 5.0; N, 1.5. Found: C,
71.8; H, 5.0; N, 1.6%.
PPh3] ppm. 1H NMR (CDCl3): 5.96 [t, (H12)L1, 1H,
JHH = 7.1 Hz], 6.23 [dd, (H6)L, 1H, JHH = 8.0 Hz,
JHH = 1.74 Hz], 6.4 [t, (H10)L1, 1H, JHH = 8.7 Hz],
6.68 [s(br), Hb, 1H], 6.95–7.55 [m, PC6H5 +
C6H5 + (H3,4,5,7,11,13)L1, 30H + 5H + 6H] ppm. FAB-
MS m/z (abundance) = 1087 (0.1) [M]+, 856 (0.7)
[M ꢀ L1]+. Anal. Calc. for C66H50ClNO2P2Ru Æ 1.25-
CH2Cl2: C, 67.7; H, 4.4; N, 1.2. Found: C, 67.4; H,
4.6; N, 0.9%.
2.2.8. Preparation of [Ru(CH@CHC6H4Me-4)(L2)
(CO)(PPh3)2] (7)
2.2.10. Preparation of [Ru(CH@CHC6H4Me-4)(L4)
(CO)(PPh3)2] (9)
[Ru(CH@CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (100
mg, 0.106 mmol) and salicylaldehyde (HL2) (14 mg,
0.115 mmol) were dissolved in dichloromethane (20
mL) and treated with sodium methoxide (11 mg, 0.204
mmol) in ethanol (10 mL). A colour change was ob-
served from deep red to yellow. The mixture was stirred
for 1 h and the solvent volume reduced until precipita-
tion of the product had started. The flask was kept at
ꢀ20 ꢁC for 3 h and the resulting bright yellow precipi-
tate filtered, washed with water (5 mL), cold ethanol
(5 mL) and hexane (10 mL). Yield: 63 mg (67%). IR
(KBr/nujol): 1913 [m(CO)], 1615, 1575, 1341, 1316,
[Ru(CH@CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (100
mg, 0.106 mmol) and 2-hydroxy-4-methylquinoline
(HL4) (18 mg, 0.113 mmol) were dissolved in dichloro-
methane (20 mL) and ethanol (10 mL). Potassium
hydroxide (12 mg, 0.214 mmol) was added and the mix-
ture was stirred for 30 min. The solvent volume was
reduced until precipitation of a colourless microcrystal-
line product was complete. This was washed with water
(5 mL), ethanol (5 mL) and hexane (10 mL). Yield:
75 mg (76%). IR (KBr/nujol): 1908, 1894 [m(CO)], 1634,
1549, 1312, 1263, 1198, 972, 849 cmꢀ1
(C6D6): 36.3 [s, PPh3] ppm. H NMR (C6D6): 1.88 [s,
CH3(L4), 3H], 2.09 [s, CH3(vinyl), 3H], 4.48 [d, L4, 1H,
JHH unresolved], 5.65 [s, H3(L4), 1H], 6.41 [d, Hb, 1H,
.
31P NMR
1278, 1179, 1145, 966, 903, 833 cmꢀ1
.
(CDCl3): 30.9 [s, PPh3] ppm. H NMR (CDCl3): 2.17
31P NMR
1
1
[s, CH3, 3 H], 5.97 [m, Hb + H2/6(L2), 1H + 1H], 6.30

3222
J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
JHH = 16.2 Hz], 6.58, 6.80 [AB, C6H4, 4H, JAB = 7.7 Hz],
6.91, 7.55 [m · 2, C6H5, 30 H], 7.22 [m, L4, 3H], 8.18 [dt,
Ha, 1H, JHH = 16.2 Hz, JHP = 2.5 Hz] ppm. FAB-MS
m/z (abundance) = 929 (4) [M]+, 812 (3) [M ꢀ vinyl]+,
667 (6) [M ꢀ PPh3]+, 639 (3) [M ꢀ CO ꢀ PPh3]+. Anal.
Calc. for C56H47NO2P2Ru Æ 1.25CH2Cl2: C, 66.4; H,
4.8; N, 1.4. Found: C, 66.8; H, 4.9; N, 1.3%.
3. Results and discussion
3.1. Preparation and characterisation of L1
The Schiff base ligand, 2-chlorophenylsalicylaldimine
(L1), shown in Chart 1, was readily prepared from the
reaction of 2-choroaniline and salicylaldehyde in etha-
nol in high yield.
2.3. X-ray crystallography
The ligand was characterised by one- and two-
dimensional 1H and 13C NMR spectroscopy, mass spec-
trometry and elemental analysis. All protons and carbon
nuclei were assigned using heteronuclear multiple quan-
tum correlation (HMQC), heteronuclear multiple bond
correlation (HMBC) and nuclear overhauser enhance-
ment (NOE) experiments. The imine proton resonates
in the characteristic region for such features at 8.56 ppm
while the hydroxy proton appears as a singlet at 13.24
ppm. The chemical shift and independence of concentra-
tion of this resonance indicates that intermolecular
hydrogen bonding does not occur in solution. Instead,
an intramolecular 6-membered interaction is more
likely, as has been reported in recent structural [56] and
spectroscopic [57] studies of Schiff bases.
Crystals of complex 3 were grown by slow diffusion
of a dichloromethane solution of the complex into
ethanol. A single crystal was mounted on a glass fibre
and all geometric and intensity data were taken from
this sample on a Bruker SMART APEX CCD dif-
fractometer using graphite-monochromated Mo Ka
˚
radiation (k = 0.71073 A) at 150 2 K. Data reduction
and integration was carried out with SAINT+ and
absorption corrections applied using the programme
SADABS. The structure was solved by direct methods
and developed using alternating cycles of least-squares
refinement and difference-Fourier synthesis. All non-
hydrogen atoms were refined anisotropically. Hydro-
gen atoms were placed in calculated positions and
their thermal parameters linked to those of the atoms
to which they were attached (riding model). Structure
solution and refinement used the SHELXTL PLUS V6.10
program package [55]. See Table 1 for selected crystal
data.
3.2. Preparation of hydride complexes of L1
An alternative to the coordinatively unsaturated
starting complexes [RuRCl(CO)(PPh3)3] (R = hydride,
vinyl) is provided by the use of the 2,1,3-benzoselen-
adiazole (BSD) complexes [RuRCl(CO)(BSD)(PPh3)2]
[52,53] These avoid contamination by free triphenyl-
phosphine and generate microcrystalline starting com-
plexes of excellent purity which can be easily
(re)crystallised from dichloromethane–ethanol mixtures.
BSD is no longer commercially available, however, we
have found that the sulfur analogue, 2,1,3-benzothi-
adiazole (BTD), can be used without compromising
the advantages mentioned above. Dropwise addition
of an ethanolic solution of sodium methoxide to a
dichloromethane solution of HL1 and the dark green hy-
dride complex [RuHCl(CO)(BTD)(PPh3)3] in dichloro-
methane led to a gradual colour change to yellow.
After stirring for 1 h, ethanol was added and the solvent
volume reduced to provide a yellow product (Scheme 1).
A clean reaction to give a single product containing
trans phosphines was indicated by a new broad singlet
Table 1
Crystal data for compound 3
3 Æ 2CH2Cl2
Chemical formula
Formula weight
Crystal system
C59H48Cl3NO2P2Ru
1072.34
triclinic
Crystal colour
yellow
0.44 · 0.38 · 0.12
Crystal size (mm)
Space group
Unit cell dimensions
ꢀ
P1
˚
a (A)
11.7683(8)
13.2497(9)
17.5273(12)
82.1570(10)
77.6070(10)
71.3950(10)
2523.0(3)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Calculated density (g/cm3)
T (K)
1.412
150(2)
l(Mo Ka) (mmꢀ1
F(000)
)
0.578
1100
22473
Reflections collected
Unique reflections (Rint
R1 (I > 2r(I))
)
11633 (0.0183)
0.0343
0.0887
wR02 (all dataꢀ) 3
˚
Residual e A (max, min)
1.057, ꢀ0.827
Scheme 1. (i) C13H10ClNO (HL1), NaOMe.

J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
3223
resonance in the 31P NMR spectrum at 58.5 ppm. Infra-
red spectroscopic analysis showed an intense m(CO)
absorption at 1906 cmꢀ1 due to the carbonyl ligand
and a band of weaker intensity which was attributed
to the hydride ligand at 1975 cmꢀ1. Confirmation of
the retention of the hydride ligand was provided by
pound reacts readily with HL1 under the same condi-
tions as described above to give the complex
[Ru(CH@CHPh)(L1)(CO)(PPh3)2] (3), as shown in
Scheme 2. The vinyl ligand was identified by the charac-
teristic resonances for the a- and b-protons at 8.25 and
3
5.79 ppm, respectively. In addition to JHH coupling
1
the H NMR spectrum of the complex which displayed
(16.9 Hz), Ha showed coupling to the mutually trans
phosphorus nuclei (3.1 Hz) to appear as a doublet of
triplets. In contrast to the spectra for the hydride com-
plexes 1 and 2, the spectroscopic features associated
with the L1 ligand are largely obscured by those of the
vinyl and phosphine substituents. Slow diffusion of eth-
anol into a dichloromethane solution of complex 3
yielded single crystals suitable for an X-ray study. The
structure is shown in Fig. 1.
This reveals the Schiff base ligand to coordinate in a
bidentate fashion with the 6-membered chelate coplanar
with the carbon ligand and C2 and C3 of the vinyl li-
gand. The 2-chlorophenyl substituent of L1, however,
is twisted by approximately 45ꢁ out of this plane. This
orientation is likely to be the cause of the inequivalence
of the phosphorus nuclei which is manifested as an AB
system in the 31P NMR spectrum. The overall structure
is essentially octahedral around Ru1. The cis-interligand
angles are in the range 84.35(6)–101.21(7)ꢁ with the O2–
Ru1–N1 bite angle of the bidentate chelate measuring
a high field hydride triplet resonance at d ꢀ10.77 ppm
showing coupling to the two phosphorus nuclei of
21.4 Hz. The fine structure of this triplet of doublets
revealed a 2.90 Hz coupling through the ruthenium
centre to the imine proton (H7) of the Schiff base ligand
(see Chart 1). This coupling was also observed for the
H7 resonance at 7.54 ppm. The eight other resonances
associated with the ligand were observed at chemical
shift values shifted downfield with respect to the corre-
sponding features in the free ligand. The fast atom bom-
bardment mass spectrum provided clear evidence for the
overall composition with a molecular ion at m/z = 884
and fragmentation due to [M – L1]+ at m/z = 653. Along
with elemental analysis data, this confirmed that the
chloride and BTD ligands had been replaced by L1 to
yield [RuH(L1)(CO)(PPh3)2] (1). In the initial stages of
this work, the complex [RuH(L)(CO)(PPh3)2], formed
from phenylsalicylaldimine (HL) was reported [58].
However, no spectroscopic data were given. The
osmium analogue [59] of the versatile ruthenium com-
plex [RuHCl(CO)(PPh3)3] [3] is far less reactive. This
stems from the reluctance of the complex to lose a phos-
phine ligand in solution, in contrast to the ruthenium
species. This drawback is circumvented by the use of
the osmium compound [OsHCl(CO)(BTD)(PPh3)2],
which provides a convenient entrypoint into osmium(II)
hydride and vinyl chemistry [38e, 45] Thus, treatment of
[OsHCl(CO)(BTD)(PPh3)2] with HL1 and sodium
methoxide resulted in an orange compound which was
formulated as the osmium analogue of complex 1. The
31P NMR spectrum of the product [OsH(L1)(CO)-
(PPh3)2] (2) revealed an AB system at 18.0 and 27.3 with
a coupling between the phosphorus nuclei of 320 Hz.
This suggested that the Schiff base ligand must render
the phosphines inequivalent. This can be explained by
hindrance to the rotation of the 2-chlorophenyl substitu-
ent of L1. Heating the sample (in C6D6) to 60 ꢁC resulted
in a singlet resonance being obtained at 21.8 ppm. The
31P NMR spectra of all the complexes discussed here
bearing the L1 ligand displayed broadened singlet
resonances at 25 ꢁC indicating that the coalescence tem-
perature for the osmium complex (2) is significantly
higher than for the ruthenium species.
3.3. Preparation of vinyl complexes of L1
Hydrometallation of phenylacetylene by [RuHCl
(CO)(BTD)(PPh3)2]
[Ru(CH@CHPh)Cl(CO)(BTD)(PPh3)2] [53]. This com-
yields
the
vinyl
complex
Scheme 2. (i) C13H10ClNO (HL1), NaOMe; (ii) C7H6O2 (HL2),
NaOMe; (iii) C9H7NO (HL3), NaOMe; (iv) C10H9NO (HL4), NaOMe.

3224
J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
which gave rise to an AB system at 6.40 and 6.95 ppm
(JAB = 7.5 Hz) and a singlet resonance at 2.21 ppm.
Hydrometallation of 3,3-dimethylbut-1-yne with
[RuHCl(CO)(BTD)(PPh3)2] provided the complex
[Ru(CH@CHtBu)Cl(CO)(BTD)(PPh3)2] in good yield.
Subsequent addition (without isolation, if desired) of
HL1 and NaOMe in dichloromethane and ethanol affords
[Ru(CH@CHtBu)(L1)(CO)(PPh3)2] (5). A large singlet
resonance at 0.37 ppm was assigned to the tertiarybutyl
substituent of the vinyl ligand, while 3JHH (16.8 Hz) and
4JHP (2.0 Hz) couplings lead to an unusually well-defined
doublet of triplets for the vinylic b-proton. A significantly
larger coupling of 3.3 Hz was observed between the phos-
phorus nuclei and the a-proton at 8.13 ppm indicating
their closer mutual proximity. A disubstituted analogue
[Ru{C(C„CPh)@CHPh}(L1)(CO)(PPh3)2] (6) was also
prepared from the enynyl complex [Ru{C(C„CPh)-
@CHPh}Cl(CO)(BTD) (PPh3)2] in good yield.
Fig. 1. Structure of [Ru(CH@CHPh)(L1)(CO)(PPh3)2] (3). Selected
bond lengths (A) and angles (ꢁ): Ru1–C1 = 1.8134(18), Ru1–C2 =
˚
3.4. Preparation of vinyl complexes of L2–L4
2.0380(18), Ru1–O2 = 2.0998(13), Ru1–N1 = 2.2217(15), Ru1–P1 =
2.4078(5), Ru1–P2 = 2.4198(5), N1–C17 = 1.304(2), O2–C11 = 1.303
(2), C2–C3 = 1.338(3), C11–C16 = 1.423(3), C16–C17 = 1.432(3), C1–
Ru1–C2 = 88.37(7), C2–Ru1–O2 = 84.35(6), C1–Ru1–N1 = 101.21(7),
O2–Ru1–N1 = 86.08(5), C1–Ru1–P1 = 89.31(6), C2–Ru1–P1 = 91.05
(5), O2–Ru1–P1 = 90.20(4), N1–Ru1–P1 = 91.00(4), C1–Ru1–P2 =
93.00(6), C2–Ru1–P2 = 84.42(5), O2–Ru1–P2 = 86.92(4), N1–Ru1–
P2 = 93.07(4), P1–Ru1–P2 = 174.847(16), C3–C2–Ru1 = 134.89(14).
The precursor to the Schiff base ligand HL1 is salicyl-
aldehyde (HL2) which can be deprotonated to act as an
asymmetrical 3-electron O/O-donor. This ligand was
found to react cleanly with [Ru(CH@CHC6H4Me-
4)Cl(CO)(BTD)- (PPh3)2] by displacement of chloride
and BTD ligands to provide [Ru(CH@CHC6H4Me-
4)(L2)(CO)(PPh3)2] (7) as shown in Scheme 2. The most
distinctive spectral feature of the 6-membered metallacy-
cle formed by coordination of L2 was the CHO proton
resonance at 8.12 ppm, which overlapped with the dou-
blet of triplets for Ha at 8.10 ppm (JHH = 16.2 Hz,
JHP = 2.8 Hz).
86.08(5)ꢁ, which is the second smallest angle in the
6-membered ring after that for C2–Ru1–O2 [84.35(6)ꢁ].
No significant deviation from the plane formed by
Ru1–N1–C17–C16–C11–O2 is observed. The C17–N1
˚
˚
distance of 1.304(2) A is comparable to that of 1.295 A
found in the literature complex [Ru(j2-p-OC6H4-
CH@NC6H4OMe-4)Cl(g6-p-cymene)] reported by Beck
and co-workers [60]. Both the Ru1–O2 bond length of
In order to extend these investigations to smaller che-
late sizes, 8-hydroxyquinoline (HL3) was employed as a
mixed-donor N/O-ligand. Deprotonation of HL3 in the
presence of [Ru(CH@CHC6H4Me-4)Cl(BTD)(CO)-
(PPh3)2] led to the isolation of a microcrystalline com-
plex which gave rise to new spectroscopic features in
˚
˚
2.0998(13) A and the Ru1–N1 distance of 2.2217(15) A
in 3 are significantly longer than the corresponding fea-
tures in the para-cymene complex of 2.045(2) and
1
˚
2.133(3) A, respectively. The bite angle of the chelate
the H NMR spectrum at 6.17, 6.32 and 7.88 ppm in
in the literature complex is significantly smaller
[79.00(10)ꢁ]. The difference in Ru1–O2 and Ru–N1 dis-
tances reflects the differing trans influence of the CO
and vinyl ligands in 3 compared to para-cymene in the
addition to the resonances for the vinyl ligand, which
were essentially unchanged from the precursor. These
were assigned as resulting from three of the six protons
of the coordinated L3 ligand, with the remainder ob-
scured by the resonances arising from the triphenylphos-
phine ligands. Elemental analysis and fast atom
bombardment (FAB) mass spectrometry led to the com-
plex being formulated as [Ru(CH@CHC6H4Me-
4)(L3)(CO)(PPh3)2] (8) with the L3 ligand forming a
5-membered chelate with the ruthenium centre. In a sim-
ilar fashion, 2-hydroxy-4-methylquinoline (HL4) was al-
lowed to react with the same precursor to yield
[Ru(CH@CHC6H4Me-4)(L4)(CO)(PPh3)2] (9). The pres-
ence of the mixed-donor ligand was indicated by four
new resonances, of which, that corresponding to the
methyl substituent at 1.88 ppm was most diagnostic.
˚
literature complex. The Ru1–C2 [2.0380(18) A] and
˚
C2–C3 [1.338(3) A] distances are similar to those re-
ported for the styrenyl ligand in the formate complex
[Ru(CH@CHPh)(j2-O2CH)(CO)L2] of 2.036(8) and
˚
1.35(1) A, respectively [43a]. The other structural
features associated with the vinyl ligand are
unremarkable.
The complex [Ru(CH@CHC6H4Me-4)(L1)(CO)-
(PPh3)2] (4) was prepared in an analogous fashion to 3
but in slightly improved yield. The spectroscopic data
for this complex were found to be similar to those for 3
apart from those associated with the tolyl substituent,

J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
3225
[5] M.R. Torres, A. Vegas, A. Santos, J. Ros, J. Organomet. Chem.
309 (1986) 169.
The overall composition of complex 9 was provided by
elemental analysis and mass spectrometry. The singlets
obtained in the 31P NMR spectra for products 7–9 were
sharp and betrayed no fluxional behaviour, suggesting
that the ligands L1–L3 adopt the expected planar
geometry.
[6] S. Jung, K. Ilg, C.D. Brandt, J. Wolf, H. Werner, Eur. J. Inorg.
Chem. (2004) 469.
[7] S. Jung, C.D. Brandt, J. Wolf, H. Werner, J. Chem. Soc., Dalton
Trans. (2004) 375.
´
[8] H. Werner, S. Jung, P. Gonzalez-Herrero, K. Ilg, J. Wolf, Eur. J.
Inorg. Chem. (2001) 1957.
[9] S. Jung, K. Ilg, J. Wolf, H. Werner, Organometallics 20 (2001)
2121.
[10] H. Werner, W. Stuer, S. Jung, B. Weberndo¨rfer, J. Wolf, Eur. J.
¨
4. Conclusions
Inorg. Chem. (2002) 1076.
[11] H. Werner, A. Stark, P. Steinert, C. Grunwald, J. Wolf, Chem.
Ber. 128 (1995) 49.
A Schiff base ligand has been prepared and fully char-
acterised by two-dimensional NMR techniques. Along
with three other ligands, the Schiff base was used to pre-
pare a new family of hydride and vinyl complexes bear-
ing 4-, 5- and 6-membered mixed-donor chelates, all of
which are bonded through oxygen and nitrogen donors.
The structure of the first example of a ruthenium vinyl
complex supported by a Schiff base ligand is reported
and used to explain the fluxional behaviour observed
in the 31P NMR spectra obtained. The potential for
hemilability in these complexes will now be investigated
in our laboratory.
[12] R. Castarlenas, M.A. Esteruelas, E. On˜ate, Organometallics 20
(2001) 2294.
´ ´
[13] M.A. Esteruelas, C. Garcıa-Yebra, M. Olivan, E. On˜ate, M.
Tajada, Organometallics 19 (2000) 5098.
[14] R. Castarlenas, M.A. Esteruelas, E. On˜ate, Organometallics 19
(2000) 5454.
´ ´
[15] M.L. Buil, M.A. Esteruelas, C. Garcıa- Yebra, E. Gutierrez-
´
Puebla, M. Olivan, Organometallics 19 (2000) 2184.
[16] C. Bohanna, M.L. Buil, M.A. Esteruelas, E. On˜ate, C. Valero,
Organometallics 18 (1999) 5176.
[17] C. Bohanna, B. Callejas, A.J. Edwards, M.A. Esteruelas, F.J.
Lahoz, L.A. Oro, N. Ruiz, C. Valero, Organometallics 17 (1998)
373.
´ ´
[18] M.A. Esteruelas, A.V. Gomez, A.M. Lopez, E. On˜ate, Organo-
metallics 17 (1998) 3567.
[19] M.A. Esteruelas, F. Liu, E. On˜ate, E. Sola, B. Zeier, Organomet-
allics 16 (1997) 2919.
5. Supplementary material
[20] M.L. Buil, S. Elipe, M.A. Esteruelas, E. On˜ate, E. Peinado, N.
Ruiz, Organometallics 16 (1997) 5748.
Crystallographic data for the structure of complex 3
have been deposited with the Cambridge Crystallo-
graphic Data Centre, CCDC 260974. Copies of the data
can be obtained free of charge on application to The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK, fax: int. code +44 1223 336 033, e-mail for in-
quiry: fileserv@ccdc.cam.ac.uk).
[21] M.A. Esteruelas, F.J. Lahoz, E. On˜ate, L.A. Oro, E. Sola, J. Am.
Chem. Soc. 118 (1996) 89.
´
[22] C. Bohanna, M.A. Esteruelas, J. Herrero, A.M. Lopez, L.A. Oro,
J. Organomet. Chem. 498 (1995) 199.
[23] C. Bohanna, M.A. Esteruelas, F.J. Lahoz, E. On˜ate, L.A. Oro,
E. Sola, Organometallics 14 (1995) 4825.
[24] C. Bohanna, M.A. Esteruelas, F.J. Lahoz, E. On˜ate, L.A. Oro,
Organometallics 14 (1995) 4685.
´
[25] B. Gomez-Lor, A. Santos, M. Ruiz, A.M. Echavarren, Eur. J.
Inorg. Chem. (2001) 2305.
[26] A.M. Castan˜o, A.M. Echavarren, J. Lopez, A. Santos, J.
Acknowledgements
´
Organomet. Chem. 379 (1989) 171.
[27] J. Montoya, A. Santos, A.M. Echavarren, J. Ros, J. Organomet.
Chem. 390 (1990) C57.
J.D.E.T.W.-E. gratefully acknowledges the Ramsay
Memorial Trust for provision of a Fellowship. We
thank the Department of Chemistry and the University
of London Central Research Fund for funding for con-
sumables and Johnson Matthey Ltd. for a generous loan
of ruthenium salts. We thank Dr. A. Aliev for discus-
sions of NMR data.
[28] H. Loumrhari, J. Ros, M.R. Torres, A. Santos, A.M. Echavarren,
J. Organomet. Chem. 411 (1991) 255.
´
[29] J. Montoya, A. Santos, J. Lopez, A.M. Echavarren, J. Ros, A.
Romero, J. Organomet. Chem. 426 (1992) 383.
´
[30] J. Lopez, A. Romero, A. Santos, A. Vegas, A.M. Echavarren, P.
Noheda, J. Organomet. Chem. 373 (1989) 249.
[31] A. Pedersen, M. Tilset, K. Folting, K.G. Caulton, Organometal-
lics 14 (1995) 875.
[32] A.V. Marchenko, H. Ge´rard, O. Eisenstein, K.G. Caulton, New.
J. Chem. 25 (2001) 1244.
References
´
[33] A.V. Marchenko, H. Gerard, O. Eisenstein, K.G. Caulton, New.
J. Chem. 25 (2001) 1382.
[1] For an overview of hydride and vinyl chemistry of ruthenium(II),
see A.F. Hill, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 7, Pergamon,
Oxford, 1995.
[34] R.A. Sanchez-Delgado, A. Andriollo, O.L. De Ochoa, T. Suarez,
N. Valencia, J. Organomet. Chem. 209 (1981) 77.
[35] A.M. Echavarren, J. Lo´pez, A. Santos, J. Montoya, J. Organo-
met. Chem. 414 (1991) 393.
[2] M.A. Esteruelas, H. Werner, J. Organomet. Chem. 303 (1986)
221.
[36] R.B. Bedford, A.F. Hill, A.R. Thompsett, A.J.P. White, D.J.
Williams, Chem. Commun. (1996) 1059.
[3] K.R. Laing, W.R. Roper, J. Chem. Soc. A (1970) 2149.
[4] H. Werner, M.A. Esteruelas, H. Otto, Organometallics 5 (1986)
2295.
[37] H. Katayma, M. Nagao, R. Moriguchi, F. Ozawa, J. Organomet.
Chem. 676 (2003) 49.

3226
J.D.E.T. Wilton-Ely et al. / Inorganica Chimica Acta 358 (2005) 3218–3226
´
[46] R. Hernandez-Molina, A. Mederos, in: J. McCleverty, T.J. Meyer
(Eds.), Comprehensive Coordination Chemistry II, vol. 1, Else-
vier, 2004.
[38] (a) A.F. Hill, A.J.P. White, D.J. Williams, J.D.E.T. Wilton-Ely,
Organometallics 17 (1998) 4249;
(b) J.C. Cannadine, A.F. Hill, A.J.P. White, D.J. Williams, J.-
D.E.T. Wilton-Ely, Organometallics 15 (1996) 5409;
(c) A.F. Hill, A.J.P. White, D.J. Williams, J.D.E.T. Wilton-Ely,
unpublished results;
[47] M. Calligaris, L. Randaccio, in: G. Wilkinson (Ed.), Comprehen-
sive Coordination Chemistry, vol. 2, Pergamon, 1987.
[48] M. Brookhart, L.K. Johnson, S.D. Ittel, Chem. Rev. 100(2000)1169.
[49] (a) F. Calderazzo, C. Floriani, R. Henzi, F. LꢀEplattenier, J.
Chem. Soc. A (1969) 1378;
(d) A.F. Hill, C.T. Ho, J.D.E.T. Wilton-Ely, Chem. Commun.
(1997) 2207;
(e) A.F. Hill, J.D.E.T. Wilton-Ely, J. Chem. Soc., Dalton Trans.
(1998) 3501.
´ ´ ´
[39] A. Santos, J. Lopez, A. Galan, J.J. Gonzalez, P. Tinoco, M.A.
(b) K.S. Finney, G.W. Everett, Inorg. Chim. Acta 11 (1974) 183;
(c) G. Henrici-Olive, S. Olive, J. Mol. Cat. 1 (1976) 121;
(d) J.R. Thornback, G. Wilkinson, J. Chem. Soc., Dalton Trans.
(1978) 110.
Echavarren, Organometallics 16 (1997) 3482.
´
[40] A. Santos, J. Lopez, J. Montoya, P. Noheda, A. Romero, A.M.
[50] (a) C.-M. Che, J.-S. Huang, Coord. Chem. Rev. 242 (2003) 97;
(b) J.A. Miller, W. Jin, S.T. Nguyen, Angew. Chem., Int. Ed.
Engl. 41 (2002) 2953;
Echavarren, Organometallics 13 (1994) 3605.
[41] A. Romero, A. Vegas, A. Santos, M. Martinez-Ripoll, J.
Organomet. Chem. 319 (1987) 103.
(c) B. De Clercq, F. Verpoort, Macromolecules 35 (2002) 8943;
(d) R. Schumacher, F. Dammast, H.-U. Reißig, Chem. Eur. J. 3
(1997) 614.
´
[42] J. Lopez, A. Santos, A. Romero, A.M. Echavarren, J. Organomet.
Chem. 443 (1993) 221.
[43] (a) H. Loumrhari, L. Matas, J. Ros, M.R. Torres, A. Perales, J.
Organomet. Chem. 403 (1991) 373;
[51] M.J. Clarke, Coord. Chem. Rev. 232 (2002) 69.
[52] The complexes were prepared by substituting BTD for BSD in the
experimental procedure reported in N.W. Alcock, A.F. Hill, M.S.
Roe, J. Chem. Soc., Dalton Trans. (1990) 1737.
(b) M.R. Torres, A. Perales, H. Loumrhari, J. Ros, J. Organomet.
Chem. 384 (1990) C61;
´
(c) H. Loumrhari, J. Ros, R. Yan˜ez, M.R. Torres, J. Organomet.
Chem. 408 (1991) 233;
[53] Complexes obtained by substitution of BTD for BSD in the
experimental procedure reported in M.C.J. Harris, A.F. Hill,
Organometallics 10 (1991) 3903.
(d) M.R. Torres, A. Perales, H. Loumrhari, J. Ros, J. Organomet.
Chem. 385 (1990) 379;
[54] A.F. Hill, M.C.J. Harris, R.P. Melling, Polyhedron 11 (1992) 781.
[55] SHELTXTL V 6.10 Bruker AXS 2000.
(e) H. Loumrhari, J. Ros, M.R. Torres, Polyhedron 10 (1991) 421;
(f) A.L. Hector, A.F. Hill, J. Organomet. Chem. 447 (1993) C7;
(g) R.B. Bedford, C.S.J. Cazin, J. Organomet. Chem. 598 (2000) 20;
(h) H. Adams, P.E. McHugh, M.J. Morris, S.E. Spey, P.J. Wright,
J. Organomet. Chem. 619 (2001) 209.
[56] S. Thamotharan, V. Parthasarathi, S.M. Anitha, A. Prasad, T.R.
Rao, A. Linden, Acta Crystallogr., Sect. E 59 (2003) 1856.
[57] W. Schilf, B. Kamienski, A. Szady-Chelmieniecka, E. Grech, J.
Mol. Struct. 700 (2004) 105.
[44] P.J. Pogorzelec, D.H. Reid, D.A. Tocher, J.D.E.T. Wilton-Ely,
Z. Naturforsch. 59b (2004) 1.
[58] H. Sasabe, S. Nakanishi, T. Takata, Inorg. Chem. Commun. 6
(2003) 1140.
[45] J.D.E.T. Wilton-Ely, S.J. Honarkhah, M. Wang, D.A. Tocher,
A.M.Z. Slawin, J. Chem. Soc., Dalton Trans. (2005) 1930.
[59] L. Vaska, J. Am. Chem. Soc. 86 (1964) 1943.
[60] O. Briel, A. Fehn, K. Polborn, W. Beck, Polyhedron 18 (1998) 225.